Green chemistry and the ten commandments of sustainability

GREEN CHEMISTRY
Air

Life

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Wat

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Ea

T
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n

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y

AND THE TEN COMMANDMENTS OF
SUSTAINABILITY
Stanley E. Manahan


ChemChar Research, Inc.
2005

THE ELEMENTS
Atomic
number
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26

27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56

Name

Symbol

Hydrogen
Helium
Lithium
Beryllium
Boron
Carbon
Nitrogen
Oxygen
Fluorine
Neon
Sodium
Magnesium
Aluminum
Silicon
Phosphorus
Sulfur
Chlorine
Argon
Potassium
Calcium
Scandium
Titanium
Vanadium
Chromium
Manganese

Iron
Cobalt
Nickel
Copper
Zinc
Gallium
Germanium
Arsenic
Selenium
Bromine
Krypton
Rubidium
Strontium
Yttrium
Zirconium
Niobium
Molybdenum
Technetium
Ruthenium
Rhodium
Palladium
Silver
Cadmium
Indium
Tin
Antimony
Tellurium
Iodine
Xenon
Cesium

Barium

H
He
Li
Be
B
C
N
O
F
Ne
Na
Mg
Al
Si
P
S
Cl
Ar
K
Ca
Sc
Ti
V
Cr
Mn
Fe
Co
Ni

Cu
Zn
Ga
Ge
As
Se
Br
Kr
Rb
Sr
Y
Zr
Nb
Mo
Tc
Ru
Rh
Pd
Ag
Cd
In
Sn
Sb
Te
I
Xe
Cs
Ba

Atomic

mass
1.00794
4.0026
6.941
9.01218
10.811
12.011
14.0067
15.9994
18.9984
20.1797
22.9898
24.305
26.98154
28.0855
30.973
32.066
35.4527
39.948
39.0983
40.078
44.9559
47.88
50.9415
51.9961
54.938
55.847
58.9332
58.6934
63.546

65.39
69.723
72.61
74.9216
78.96
79.904
83.8
85.4678
87.62
88.9056
91.224
92.9064
95.94
98
101.07
102.9055
106.42
107.8682
112.411
114.82
118.710
121.757
127.60
126.9045
131.29
132.9054
137.327

Atomic
number

Name

Symbol

Atomic
mass

57
Lanthanum
La
138.9055
58
Cerium
Ce
140.115
59
Praseodymium Pr
140.9077
60
Neodymium Nd
144.24
61
Promethium Pm
145
62
Samarium
Sm
150.36
63

Europium
Eu
151.965
64
Gadolinium
Gd
157.25
65
Terbium
Tb
158.925
66
Dysprosium Dy
162.50
67
Holmium
Ho
164.9303
68
Erbium
Er
167.26
69
Thulium
Tm
168.9342
70
Ytterbium
Yb
173.04

71
Lutetium
Lu
174.967
72
Hafnium
Hf
178.49
73
Tantalum
Ta
180.9497
74
Tungsten
W
183.85
75
Rhenium
Re
186.207
76
Osmium
Os
190.2
77
Iridium
Ir
192.22
78
Platinum

Pt
195.08
79
Gold
Au
196.9665
80
Mercury
Hg
200.59
81
Thallium
Tl
204.383
82
Lead
Pb
207.2
83
Bismuth
Bi
208.98
84
Polonium
Po
209
85
Astatine
At
210

86
Radon
Rn
222
87
Francium
Fr
223
88
Radium
Ra
226.0254
89
Actinium
Ac
227.0278
90
Thorium
Th
232.038
91
Protactinium Pa
231.0359
92
Uranium
U
238.0289
93
Neptunium
Np

237.048
94
Plutonium
Pu
244
95
Americium
Am
243
96
Curium
Cm
247
97
Berkelium
Bk
247
98
Californium Cf
251
99
Einsteinium Es
252
100
Fermium
Fm
257.1
101
Mendelevium Md
258.1

102
Nobelium
No
255
103
Lawrencium Lr
260
104
Rutherfordium Rf
261.11
105
Dubnium
Db
262.11
106
Seaborgium Sg
263.12
107
Bohrium
Bh
262.12
108
Hassium
Hs
265
109
Meitnerium
Mt
266
________________________________________

1
Elements above atomic number 92 have been
made artificially.


GREEN CHEMISTRY
AND THE TEN COMMANDMENTS
OF SUSTAINABILITY
2nd ed

Stanley E. Manahan

2006

ChemChar Research, Inc
Publishers
Columbia, Missouri U.S.A.


Copyright © 2006 by Stanley E. Manahan
All Rights Reserved.
No part of this publication may be reproduced in any form or by any
means, electronic or mechanical, including photocopy, recording, or any
information storage and retrieval system, without permission in writing
from the publisher.

ChemChar Research, Inc.
2005 Woodlea Drive
Columbia, MO 65201 U.S.A.

International Standard Book Number: 0-9749522-4-9

Printed in the United States of America


TABLE OF CONTENTS
Chapter 1.Chemistry, Green Chemistry, and Environmental Chemistry . . . . . . . . . . . 1
1.1.Chemistry Is Good . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1
1.2.The Environment and the Five Environmental Spheres . . . . . . . . . . . . . . . . . . . . . 3
1.3.What Is Environmental Chemistry? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .5
1.4.Environmental Pollution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
1.5.What Is Green Chemistry? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .9
1.6.Green Chemistry and Synthetic Chemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
1.7.Reduction of Risk: Hazard and Exposure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .12
1.8.The Risks of No Risks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .14
1.9.Waste Prevention . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1 5
1.10.Basic Principles of Green Chemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
1.11. Some Things to Know About Chemistry before You Even Start . . . . . . . . . . . . 17
1.12.Combining Atoms to Make Molecules and Compounds . . . . . . . . . . . . . . . . . . 18
1.13.The Process of Making and Breaking Chemical Bonds: Chemical Reactions . 20
1.14.The Nature of Matter and States of Matter . . . . . . . . . . . . . . . . . . . . . . . . . . . . .22
Chapter 2.The Elements: Basic Building Blocks of Green Chemicals . . . . . . . . . . . 27
2.1.Elements, Atoms, and Atomic Theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .27
2.2.Hydrogen, the Simplest Atom . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .30
2.3.Helium, the First Noble Gas . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
2.4.Lithium, the First Metal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .35
2.5.The Second Period of the Periodic Table . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
2.6.The Special Significance of the Octet of 8 Outer Shell Electrons . . . . . . . . . . . . 33

2.7.Completing the 20-Element Periodic Table . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
2.8.The Brief Periodic Table Is Complete . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .49
Chapter 3.Compounds: Safer Materials for a Safer World . . . . . . . . . . . . . . . . . . . . 55
3.1.Chemical Bonds and Compound Formation . . . . . . . . . . . . . . . . . . . . . . . . . . . . .55
3.2.Electrons Involved in Chemical Bonds and Octets of Electrons . . . . . . . . . . . . . .57
3.3.Sodium Chloride and Ionic Bonds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58
i


3.4.Covalent Bonds in H2 and Other Molecules . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64
3.5.Covalent Bonds in Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .64
3.6.Covalent Bonds and Green Chemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
3.7.Predicting Covalently Bound Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
3.8.Chemical Formulas, the Mole, and Percentage Composition . . . . . . . . . . . . . . . .71
3.9.What Are Chemical Compounds Called? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
3.10.Acids, Bases, and Salts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 74
Chapter 4. Chemical Reactions: Making Materials Safely Without Damaging the

Environment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .81
4.1.Describing What Happens With Chemical Equations . . . . . . . . . . . . . . . . . . . . . .81
4.2.Balancing Chemical Equations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83
4.3.Just Because You Can Write It Does Not Mean That It Will Happen . . . . . . . . . .84
4.4.Yield and Atom Economy in Chemical Reactions . . . . . . . . . . . . . . . . . . . . . . . . 86
4.5.Catalysts That Make Reactions Go . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .87
4.6.Kinds of Chemical Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88
4.7.Oxidation-Reduction Reactions and Green Chemistry . . . . . . . . . . . . . . . . . . . . .90
4.8.Quantitative Information from Chemical Reactions . . . . . . . . . . . . . . . . . . . . . . .93
4.9.Stoichiometry By the Mole Ratio Method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95
4.10.Limiting Reactant and Percent Yield . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 97
4.11. Titrations: Measuring Moles By Volumes of Solution . . . . . . . . . . . . . . . . . . . 98

4.12.Industrial Chemical Reactions: The Solvay Process . . . . . . . . . . . . . . . . . . . . 102
Chapter 5.The Wonderful World Of Carbon: Organic Chemistry and Biochemicals . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .109
5.1.Rings and Chains of Carbon Atoms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109
5.2.Compounds of Carbon and Hydrogen: Hydrocarbons . . . . . . . . . . . . . . . . . . . .110
5.3.Lines Showing Organic Structural Formulas . . . . . . . . . . . . . . . . . . . . . . . . . . . 116
5.4.Functional Groups . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 118
5.5.Giant Molecules from Small Organic Molecules . . . . . . . . . . . . . . . . . . . . . . . . 123
5.6.Life Chemicals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .126
5.7.Carbohydrates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 127
5.8.Proteins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 128
5.9.Lipids: Fats, Oils, and Hormones . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .129
5.10. Nucleic Acids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 131
ii


Chapter 6.Energy Relationships . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 133
6.1.Energy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 133
6.2.Radiant Energy from the Sun . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 136
6.3.Storage and Release of Energy By Chemicals . . . . . . . . . . . . . . . . . . . . . . . . . . 140
6.4.Energy Sources . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 142
6.5.Conversions Between Forms of Energy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 144
6.6.Green Engineering and Energy Conversion Efficiency . . . . . . . . . . . . . . . . . . . 147
6.7.Conversion of Chemical Energy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 148
6.8.Renewable Energy Sources . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .150
6.9.Nuclear Energy: Will it Rise Again? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .155
Chapter 7.Water, the Ultimate Green Solvent: Its Uses and Environmental Chemistry
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .159
7.1.H2O: Simple Formula, Complex Molecule . . . . . . . . . . . . . . . . . . . . . . . . . . . . 162
7.2.Important Properties of Water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .162

7.3.Water Distribution and Supply . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 163
7.4.Bodies of Water and Life in Water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 164
7.5.Chemical Processes in Water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .167
7.6.Fizzy Water from Underground . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .168
7.7.(Weak) Acid from the Sky . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .169
7.8.Why Natural Waters Contain Alkalinity and Calcium . . . . . . . . . . . . . . . . . . . . 170
7.9.Metals in Water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 171
7.10.Water Interactions with Other Phases . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .171
7.11. Heavy Metal Water Pollutants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 173
7.12.Inorganic Water Pollutants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 175
7.13.Organic Water Pollutants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 177
7.14.Pesticides in Water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 179
7.15.Polychlorinated Biphenyls (PCBs) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .183
7.16.Radioactive Substances in Water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 185
7.17.Water Treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 185
Chapter 8.Air and the Atmosphere . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 195
8.1.More Than Just Air to Breathe . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 195
8.2.Atmospheric Chemistry and Photochemical Reactions . . . . . . . . . . . . . . . . . . . 199
iii


8.3.Energy and Mass Transfer in the Atmosphere . . . . . . . . . . . . . . . . . . . . . . . . . . 201
8.4.Atmospheric Oxygen and Nitrogen . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 204
8.5.Atmospheric Pollutant Particles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 205
8.6.Pollutant Gaseous Oxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 207
8.7.Acid Rain . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .210
8.8.Miscellaneous Gases in the Atmosphere . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .212
8.9.CO2: The Ultimate Air Pollutant? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 213
8.10.Photochemical Smog . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 217
Chapter 9.The Biosphere: How the Revolution in Biology Relates to Green

Chemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .223
9.1.Green Chemistry and the Biosphere . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 223
9.2.Biology and the Biosphere . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 224
9.3.Cells: Basic Units of Life . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .227
9.4.Metabolism and Control in Organisms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 229
9.5. Reproduction and Inherited Traits . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .233
9.6.Stability and Equilibrium of the Biosphere . . . . . . . . . . . . . . . . . . . . . . . . . . . . .233
9.7.DNA and the Human Genome . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 236
9.8.Genetic Engineering . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 240
9.9.Biological Interaction With Environmental Chemicals . . . . . . . . . . . . . . . . . . . 242
9.10.Biodegradation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 243
9.11. The Anthrosphere in Support of the Biosphere . . . . . . . . . . . . . . . . . . . . . . . . 245
Chapter 10. The Geosphere, Soil, and Food Production: The Second Green

Revolution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 251
10.1.The Solid Earth . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .251
10.2.Environmental Hazards of the Geosphere . . . . . . . . . . . . . . . . . . . . . . . . . . . . 253
10.3.Water in and on the Geosphere . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .256
10.4.Anthrospheric Influences on the Geosphere . . . . . . . . . . . . . . . . . . . . . . . . . . .258
10.5.The Geosphere as a Waste Repository . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 259
10.6.Have You Thanked a Clod Today? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 260
10.7.Production of Food and Fiber on Soil — Agriculture . . . . . . . . . . . . . . . . . . . .263
10.8.Plant Nutrients and Fertilizers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 265
10.9.Pesticides and Agricultural Production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .267
iv


10.10. Soil and Plants Related to Wastes And Pollutants . . . . . . . . . . . . . . . . . . . . . 268
10.11. Soil Loss — Desertification and Deforestation . . . . . . . . . . . . . . . . . . . . . . . 269

10.12. Agricultural Applications of Genetically Modified Organisms . . . . . . . . . . . 272
Chapter 11. Toward a Greener Anthrosphere through Industrial Ecology . . . . . . . . 279
11.1. Industrial Ecology and Industrial Ecosystems . . . . . . . . . . . . . . . . . . . . . . . . . 279
11.2. Metabolic Processes in Industrial Ecosystems . . . . . . . . . . . . . . . . . . . . . . . . . 281
11.3. Life Cycles in Industrial Ecosystems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 284
11.4. Kinds of Products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 286
11.5. Attributes Required by an Industrial Ecosystem . . . . . . . . . . . . . . . . . . . . . . . .287
11.6. Kalundborg . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 289
11.7. Environmental Impacts of Industrial Ecosystems . . . . . . . . . . . . . . . . . . . . . . 290
11.8. Green Chemistry in The Service of Industrial Ecosystems . . . . . . . . . . . . . . . 293
11.9. Feedstocks, Reagents, Media, and Catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . 296
Chapter 12. Feedstocks: Maximum Utilization of Renewable and Biological

Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 305
12.1.Sources of Feedstocks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .305
12.2.Utilization of Feedstocks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 306
12.3.Biological Feedstocks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .307
12.4.Fermentation and Plant Sources of Chemicals . . . . . . . . . . . . . . . . . . . . . . . . . 309
12.5.Glucose As Feedstock . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .312
12.6.Cellulose . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 315
12.7.Feedstocks from Cellulose Wastes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 317
12.9.Direct Biosynthesis of Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 319
12.10. Bioconversion Processes for Synthetic Chemicals . . . . . . . . . . . . . . . . . . . . 320
Chapter 13 Terrorism, Toxicity, And Vulnerability: Chemistry in Defense of

Human Welfare . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 327
13.1.Vulnerability to Terrorist Attack . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .327
13.2.Protecting the Anthrosphere . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 328
13.3.Substances That Explode, Burn, or React Violently . . . . . . . . . . . . . . . . . . . . .329
13.4.Toxic Substances and Toxicology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .331

13.5.Toxic Chemical Attack . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 335
13.6.Protecting Water, Food, and Air . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 339
v


13.7.Detecting Hazards . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .341
13.8.Green Chemistry to Combat Terrorism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .342
13.9.Green Chemistry for Sustainable Prosperity and a Safer World . . . . . . . . . . . .342
Chapter 14 The Ten Commandments of Sustainability . . . . . . . . . . . . . . . . . . . . . . 347
14.1.We Cannot Go On Like This. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 347
14.2.The First Commandment. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 349
14.3.The Second Commandment. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .352
14.4.The Third Commandment. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 354
14.5.The Fourth Commandment. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 356
14.6.The Fifth Commandment. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .359
14.7.The Sixth Commandment. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 360
14.8.The Seventh Commandment. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 361
14.9.The Eighth Commandment. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 362
14.10.The Ninth Commandment. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 362
14.11.The Tenth Commandment. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 363
Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .368

vi


THE AUTHOR

Stanley E. Manahan is Professor of Chemistry at the University of MissouriColumbia, where he has been on the faculty since 1965. He received his A.B. in
chemistry from Emporia State University in 1960 and his Ph.D. in analytical chemistry
from the University of Kansas in 1965. Since 1968 his primary research and professional

activities have been in environmental chemistry, toxicological chemistry, and waste
treatment. His classic textbook, Environmental Chemistry, 8th ed (CRC Press, Boca
Raton, Florida, 2004) has been in print continuously in various editions since 1972
and is the longest standing title on this subject in the world. Other books that he has
written are Environmental Science and Technology, 2nd ed., (Taylor & Francis, 2006),
Toxicological Chemistry and Biochemistry, 3rd ed. (CRC Press/Lewis Publishers, 2001),
Fundamentals of Environmental Chemistry, 2nd ed. (CRC Press/Lewis Publishers,
2001), Industrial Ecology: Environmental Chemistry and Hazardous Waste (CRC
Press/Lewis Publishers, 1999), Environmental Science and Technology (CRC Press/
Lewis Publishers, 1997), Hazardous Waste Chemistry, Toxicology and Treatment (Lewis
Publishers, 1992), Quantitative Chemical Analysis, (Brooks/Cole, 1986), and General
Applied Chemistry, 2nd ed. (Willard Grant Press, 1982). He has lectured on the topics of
environmental chemistry, toxicological chemistry, waste treatment, and green chemistry
throughout the U.S. as an American Chemical Society Local Section Tour Speaker, and
has presented plenary lectures on these topics in international meetings in Puerto Rico;
the University of the Andes in Mérida, Venezuela, Hokkaido University in Japan, the
National Autonomous University in Mexico City, France, and Italy. He was the recipient
of the Year 2000 Award of the Environmental Chemistry Division of the Italian Chemical
Society. His research specialty is gasification of hazardous wastes.

vii


viii


PREFACE
Green Chemistry and the Ten Commandments of Sustainability, 2nd ed, was
written to provide an overview of the emerging discipline of green chemistry along
with the fundamental chemical principles needed to understand this science. The second

edition follows the first edition published in 2004 under the title of Green Chemistry:
Fundamentals of Sustainable Chemical Science and Technology, from which it differs
by the inclusion of an additional chapter, Chapter 14, “The Ten Commandments of
Sustainability.” The year 2005 may well represent a “tipping point” with respect
to sustainability. Extreme weather events, though not proof of global warming, are
consistent with significant human effects upon global climate. Catastrophic events,
such as Hurricane Katrina, which devastated the U.S. Gulf Coast and New Orleans,
have shown the vulnerability of fragile modern infrastructures and may portend future
disasters intensified by global climate change. The tremendous shrinkage of the Arctic
ice cap evident during recent years provides an additional indication of global climate
change. Sharp increases in petroleum and natural gas prices show that Earth is running
out of these fossil fuel resources upon which modern economies are based.
It goes without saying that sustainability must be achieved if humankind is to survive
with any sort of reasonable living standard on Planet Earth. Chemists and chemical
science have an essential role to play in achieving sustainability. In the chemical sciences,
green chemistry has developed since the 1990s as a key to sustainability. And it is crucial
that nonchemists have an understanding of green chemistry and how it can be used to
achieve sustainability, not just for humans, but for all life forms as well, on our fragile
planet. Therefore, this book includes a basic introduction to the principles of chemistry
for those readers who may have little or no prior knowledge of this subject.
Laudable as its goals and those who work to achieve them are, green chemistry has
developed a somewhat narrow focus. For the most part, it has concentrated largely on
chemical synthesis, more specifically organic synthesis. It needs to be more inclusive of
other areas pertinent to the achievement of sustainability, such as environmental chemistry
and the science of industrial ecology. This book attempts to integrate these and other
pertinent disciplines into green chemistry. In so doing, it recognizes five overlapping
and interacting environmental spheres. Four of these have long been recognized by
practitioners of environmental science. They are (1) the biosphere, (2) the hydrosphere,
(3) the geosphere, and (4) the atmosphere. But, to be realistic, a fifth sphere must be
recognized and studied. This is the anthrosphere, which consists of all of the things

that humans have made and the systems that they operate throughout the environment.
Highways, buildings, airports, factories, cultivated land, and a huge variety of structures
and systems produced by human activities are part of Earth as we know it and must be
dealt with in any comprehensive view of the environment. A basic aspect of this book
is to deal with the five environmental spheres and to discuss how — for better or worse
— the anthrosphere is an integral part of this Earth system.
ix


Chapters 1–4 of this book introduce the basic concepts of chemistry and green
chemistry. Chapter 1, “Chemistry, Green Chemistry and Environmental Chemistry,”
includes a brief “minicourse” in chemistry that introduces the reader to fundamental
ideas of atoms, elements, compounds, chemical formulas, and chemical equations so
that the reader can have the background to understand these aspects in later chapters.
Chapter 2, “The Elements: Basic Building Blocks of Green Chemicals,” introduces the
elements and fundamentals of atomic structure. It develops an abbreviated version of
the periodic table consisting of the first 20 elements to give the reader an understanding
of this important foundation of chemistry. It also points out the green aspects of these
elements, such as elemental hydrogen as a means of energy storage and transport and
fuel for nonpolluting fuel cells. Chapter 3, “Compounds: Safer Materials for a Safer
World,” explains chemical bonding, chemical formulas, and the concept of the mole.
It points out how some chemical compounds are greener than others, for example,
those that are relatively more biodegradable compared to ones that tend to persist in
the environment. With an understanding of chemical compounds, Chapter 4. “Chemical
Reactions: Making Materials Safely Without Damaging The Environment,” discusses
how compounds are made and changed and introduces the idea of stoichiometry. It
develops some key ideas of green chemistry such as atom economy and illustrates what
makes some chemical reactions more green than others.
It is impossible to consider green chemistry in a meaningful manner without
consideration of organic chemistry. Furthermore, given the importance of biosynthesis

and the biological effects of toxic substances, it is essential to have a basic understanding
of biochemicals. These subjects are covered in Chapter 5, “The Wonderful World of
Carbon: Organic Chemistry and Biochemicals.”
Chapter 6, “Energy Relationships,” discusses the crucial importance of energy
in green chemistry. It explains how abundant, sustainable, environmentally friendly
energy sources are a fundamental requirement in maintaining modern societies in
a sustainable manner. Chapter 7, “Green Water,” discusses water resources and the
environmental chemistry of water. The environmental chemistry of the atmosphere
is covered in Chapter 8, “Air and The Atmosphere.” This chapter also explains
how the atmosphere is a sustainable source of some important raw materials, such
as nitrogen used to make nitrogen fertilizers. The biosphere is discussed in Chapter
9, “The Biosphere: How The Revolution in Biology Relates to Green Chemistry.”
Obviously, protection of the biosphere is one of the most important goals of green
chemistry. This chapter explains how the biosphere is a renewable source of some key
raw materials. The geosphere is introduced in Chapter 10. “The Geosphere, Soil, And
Food Production: The Second Green Revolution In Agriculture.” Soil and its role in
producing food and raw materials are discussed in this chapter. The concepts of the
anthrosphere and industrial ecology are covered in Chapter 11, “The Anthrosphere and
Industrial Ecology.” Feedstocks, which are required to support the chemical industry
are discussed in Chapter 12, “Feedstocks: Maximum Utilization of Renewable and
Biological Materials.” Emphasis is placed on renewable feedstocks from biological
sources in place of depletable petroleum feedstocks.
Terrorism has become a central problem of our time. A unique feature of this book
is its coverage of this topic in Chapter 13, “Terrorism, Toxicity, and Vulnerability:
Chemistry in Defense of Human Welfare.” Included are agents of terrorism such as
x


military poisons, means of detecting terrorist threats, and measures that may be taken
to reduce such threats. Because of the threats posed by toxic agents, toxicological

chemistry is introduced and discussed in this chapter.
The book concludes with Chapter 14, “The Ten Commandments of Sustainability,”
which distills the essence of sustainability into ten succinct principles. In so doing,
the chapter places green chemistry within a framework of the sustainable society that
must be developed if modern civilization is to survive with a reasonable standard of
living for humankind.
Reader feedback is eagerly solicited. Questions and suggestions may be forwarded
to the author at

xi



1 CHEMISTRY, GREEN CHEMISTRY, AND ENVIRONMENTAL
CHEMISTRY

1.1. CHEMISTRY IS GOOD
Chemistry is the science of matter. Are you afraid of chemistry? Many people are
and try to avoid it. But avoiding chemistry is impossible. That is because all matter,
all things, the air around us, the water we must drink, and all living organisms are
made of chemicals. People who try to avoid all things that they regard as chemical may
fail to realize that chemical processes are continuously being carried out in their own
bodies. These are processes that far surpass in complexity and variety those that occur
in chemical manufacturing operations. So, even those people who want to do so cannot
avoid chemistry. The best course of action with anything that cannot be avoided and that
might have an important influence on our lives (one’s chemistry professor may come to
mind) is to try to understand it, to deal with it. To gain an understanding of chemistry is
probably why you are reading this book.
Green Chemistry is written for a reader like you. It seeks to present a body of chemical
knowledge from the most fundamental level within a framework of the relationship of

chemical science to human beings, their surroundings, and their environment. Face it,
the study of chemistry based upon facts about elements, atoms, compounds, molecules,
chemical reactions, and other basic concepts needed to understand this science is found
by many to be less than exciting. However, these concepts and many more are essential to
a meaningful understanding of chemistry. Anyone interested in green chemistry clearly
wants to know how chemistry influences people in the world around us. So this book
discusses real-world chemistry, introducing chemical principles as needed.
During the approximately two centuries that chemical science has been practiced
on an ever-increasing scale, it has enabled the production of a wide variety of goods that
are valued by humans. These include such things as pharmaceuticals that have improved
health and extended life, fertilizers that have greatly increased food productivity, and
semiconductors that have made possible computers and other electronic devices. Without
the persistent efforts of chemists and the enormous productivity of the chemical industry,
nothing approaching the high standard of living enjoyed in modern industrialized
societies would be possible.


 Green Chemistry, 2nd ed
But there can be no denying that in years past, and even at present, chemistry has
been misused in many respects, such as the release of pollutants and toxic substances and
the production of nonbiodegradable materials, resulting in harm to the environment and
living things, including humans. It is now obvious that chemical science must be turned
away from emphasis upon the exploitation of limited resources and the production of
increasing amounts of products that ultimately end up as waste and toward the application
of chemistry in ways that provide for human needs without damaging the Earth support
system upon which all living things depend. Fortunately, the practice of chemical
science and industry is moving steadily in the direction of environmental friendliness
and resource sustainability. The practice of chemistry in a manner that maximizes its
benefits while eliminating or at least greatly reducing its adverse impacts has come to be
known as green chemistry, the topic of this book.

As will be seen in later chapters of this book, the practice of chemistry is divided into
several major categories. Most elements other than carbon are involved with inorganic
chemistry. Common examples of inorganic chemicals are water, salt (sodium chloride),
air pollutant sulfur dioxide, and lime. Carbon occupies a special place in chemistry
because it is so versatile in the kinds of chemical species (compounds) that it forms.
Most of the more than 20 million known chemicals are substances based on carbon
known as organic chemicals and addressed by the subject of organic chemistry. The
unique chemistry of carbon is addressed specifically in Chapter 5, “The Wonderful World
of Carbon: Organic Chemistry and Biochemicals.” The underlying theory and physical
phenomena that explain chemical processes are explained by physical chemistry. Living
organisms carry out a vast variety of chemical processes that are important in green
chemistry and environmental chemistry. The chemistry that living organisms perform is
biochemistry, which is addressed in Chapters 5 and 9. It is always important to know
the identities and quantities of various chemical species present in a system, including
various environmental systems. Often, significant quantities of chemical species are very
low, so sophisticated means must be available to detect and quantify such species. The
branch of chemistry dealing with the determination of kinds and quantities of chemical
species is analytical chemistry.
As the chemical industry developed and grew during the early and mid 1900s, most
practitioners of chemistry remained unconcerned with and largely ignorant of the potential
for harm — particularly damage to the outside environment — of their products and
processes. Environmental chemistry was essentially unknown and certainly not practiced
by most chemists. Incidents of pollution and environmental damage, which were many
and severe, were commonly accepted as a cost of doing business or blamed upon the
industrial or commercial sectors. The unfortunate attitude that prevailed is summarized
in a quote from a standard book on industrial chemistry from 1954 (American Chemical
Industry—A History, W. Haynes Van Nostrand Publishers, 1954): “By sensible definition
any by-product of a chemical operation for which there is no profitable use is a waste.
The most convenient, least expensive way of disposing of said waste — up the chimney
or down the river — is best.”

Despite their potential to cause harm, nobody is more qualified to accept
responsibility for environmental damage from chemical products or processes than are


Chap. 1, Chemistry, Green Chemistry, and Environmental Chemistry 
chemists who have the knowledge to understand how such harmful effects came about.
As the detrimental effects of chemical manufacture and use became more obvious and
severe, chemists were forced, often reluctantly, to deal with them. At present, enlightened
chemists and chemical engineers do not view the practice of environmentally beneficial
chemistry and manufacturing as a burden, but rather as an opportunity that challenges
human imagination and ingenuity.
1.2. THE ENVIRONMENT AND THE FIVE ENVIRONMENTAL SPHERES
Compared to the generally well defined processes that chemists study in the laboratory,
those that occur in the environment are rather complex and must be viewed in terms of
simplified models. A large part of this complexity is due to the fact that environmental
chemistry must take into account five interacting and overlapping compartments
or spheres of the environment, which affect each other and which undergo continual
interchanges of matter and energy. Traditionally, environmental science has considered
water, air, earth, and life — that is, the hydrosphere, the atmosphere, the geosphere,
and the biosphere. When considered at all, human activities were generally viewed as
undesirable perturbations on these other spheres, causing pollution and generally adverse
effects. Such a view is too narrow, and we must include a fifth sphere, the anthrosphere,
consisting of the things humans make and do. By regarding the anthrosphere as an
integral part of the environment, humans can modify their anthrospheric activities to do
minimal harm to the environment, or to even improve it.
Figure 1.1 shows the five spheres of the environment, including the anthrosphere,
and some of the exchanges of material between them. Each of these spheres is described
briefly below.
The atmosphere is a very thin layer compared to the size of Earth, with most
atmospheric gases lying within a few kilometers of sea level. In addition to providing

oxygen for living organisms, the atmosphere provides carbon dioxide required for plant
photosynthesis, and nitrogen that organisms use to make proteins. The atmosphere serves
a vital protective function in that it absorbs highly energetic ultraviolet radiation from
the sun that would kill living organisms exposed to it. A particularly important part of the
atmosphere in this respect is the stratospheric layer of ozone, an ultraviolet-absorbing
form of elemental oxygen. Because of its ability to absorb infrared radiation by which
Earth loses the energy that it absorbs from the sun, the atmosphere stabilizes Earth’s
surface temperature. The atmosphere also serves as the medium by which the solar
energy that falls with greatest intensity in equatorial regions is redistributed away from
the Equator. It is the medium in which water vapor evaporated from oceans as the first
step in the hydrologic cycle is transported over land masses to fall as rain over land.
Earth’s water is contained in the hydrosphere. Although frequent reports of torrential
rainstorms and flooded rivers produced by massive storms might give the impression
that a large fraction of Earth’s water is fresh water, more than 97% of it is seawater in
the oceans. Most of the remaining fresh water is present as ice in polar ice caps and
glaciers. A small fraction of the total water is present as vapor in the atmosphere. The


 Green Chemistry, 2nd ed
remaining liquid fresh water is that available for growing plants and other organisms
and for industrial uses. This water may be present on the surface as lakes, reservoirs, and
streams, or it may be underground as groundwater.
Atmosphere

r

po

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Su
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a
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,
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Anthrosphere

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d
olve
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Environmental
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r

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Geosphere

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HumusPlantnutrients

Figure 1.1. Illustration of the five major spheres of the environment. These spheres are closely tied
together, interact with each other, and exchange materials and energy. A meaningful examination of
environmental sciences must include all five of these spheres, including the anthrosphere.

The solid part of earth, the geosphere, includes all rocks and minerals. A particularly
important part of the geosphere is soil, which supports plant growth, the basis of food
for all living organisms. The lithosphere is a relatively thin solid layer extending from
Earth’s surface to depths of 50–100 km. The even thinner outer skin of the lithosphere
known as the crust is composed of relatively lighter silicate-based minerals. It is the part
of the geosphere that is available to interact with the other environmental spheres and
that is accessible to humans.
The biosphere is composed of all living organisms. For the most part, these organisms
live on the surface of the geosphere on soil, or just below the soil surface. The oceans
and other bodies of water support high populations of organisms. Some life forms exist
at considerable depths on ocean floors. In general, though, the biosphere is a very thin


Chap. 1, Chemistry, Green Chemistry, and Environmental Chemistry 
layer at the interface of the geosphere with the atmosphere. The biosphere is involved
with the geosphere, hydrosphere, and atmosphere in biogeochemical cycles through
which materials such as nitrogen and carbon are circulated.
Through human activities, the anthrosphere has developed strong interactions with
the other environmental spheres. Many examples of these interactions could be cited.
By cultivating large areas of soil for domestic crops, humans modify the geosphere and

influence the kinds of organisms in the biosphere. Humans divert water from its natural
flow, use it, sometimes contaminate it, then return it to the hydrosphere. Emissions of
particles to the atmosphere by human activities affect visibility and other characteristics
of the atmosphere. The emission of large quantities of carbon dioxide to the atmosphere
by combustion of fossil fuels may be modifying the heat-absorbing characteristics of
the atmosphere to the extent that global warming is almost certainly taking place. The
anthrosphere perturbs various biogeochemical cycles.
The effect of the anthrosphere over the last two centuries in areas such as burning
large quantities of fossil fuels is especially pronounced upon the atmosphere and has the
potential to change the nature of Earth significantly. According to Nobel Laureate Paul
J. Crutzen of the Max Planck Institute for Chemistry, Mainz, Germany, this impact is so
great that it will lead to a new global epoch to replace the halocene epoch that has been
in effect for the last 10,000 years since the last Ice Age. Dr. Crutzen has coined the term
anthropocene (from anthropogenic) to describe the new epoch that is upon us.
1.3. WHAT IS ENVIRONMENTAL CHEMISTRY?
The practice of green chemistry must be based upon environmental chemistry.
This important branch of chemical science is defined as the study of the sources,
reactions, transport, effects, and fates of chemical species in water, soil, air, and living
environments and the effects of technology thereon.1 Figure 1.2 illustrates this definition
of environmental chemistry with an important type of environmental chemical species.
In this example, two of the ingredients required for the formation of photochemical
smog — nitric oxide and hydrocarbons — are emitted to the atmosphere from vehicles
and transported through the atmosphere by wind and air currents. In the atmosphere,
energy from sunlight brings about photochemical reactions that convert nitric oxide
and hydrocarbons to ozone, noxious organic compounds, and particulate matter, all
characteristic of photochemical smog. Various harmful effects are manifested, such
as visibility-obscuring particles in the atmosphere, or ozone, which is unhealthy when
inhaled by humans, or toxic to plants. Finally, the smog products end up on soil, deposited
on plant surfaces, or in bodies of water.
Figure 1.1 showing the five environmental spheres may provide an idea of the

complexity of environmental chemistry as a discipline. Enormous quantities of materials
and energies are continually exchanged among the five environmental spheres. In
addition to variable flows of materials, there are variations in temperature, intensity
of solar radiation, mixing, and other factors, all of which strongly influence chemical
conditions and behavior.


 Green Chemistry, 2nd ed

Solarenergyisusedtotransform
primaryairpollutantstoozone
andnoxiousorganicmaterials
inphotochemicalsmog
Airpollutantstransported
totheatmosphere

Nitricoxideand
hydrocarbonsemitted
totheatmosphere

Adverseeffects,suchasreduced
visibilityfromparticlesformed
bysmog.
Fate,suchasdeposition
ontoplants

Figure 1.2. Illustration of the definition of environmental chemistry with a common environmental
contaminant.

Throughout this book the role of environmental chemistry in the practice of green

chemistry is emphasized. Green chemistry is practiced to minimize the impact of chemicals
and chemical processes upon humans, other living organisms, and the environment as a
whole. It is only within the framework of a knowledge of environmental chemistry that
green chemistry can be successfully practiced.
There are several highly interconnected and overlapping categories of environmental
chemistry. Aquatic chemistry deals with chemical phenomena and processes in water.
Aquatic chemical processes are very strongly influenced by microorganisms in the water,
so there is a strong connection between the hydrosphere and biosphere insofar as such
processes are concerned. Aquatic chemical processes occur largely in “natural waters”
consisting of water in oceans, bodies of fresh water, streams, and underground aquifers.
These are places in which the hydrosphere can interact with the geosphere, biosphere,
and atmosphere and is often subjected to anthrospheric influences. Aspects of aquatic
chemistry are considered in various parts of this book and are addressed specifically in
Chapter 7, “Green Water.”
Atmospheric chemistry is the branch of environmental chemistry that considers
chemical phenomena in the atmosphere. Two things that make this chemistry unique are the
extreme dilution of important atmospheric chemicals and the influence of photochemistry.
Photochemistry occurs when molecules absorb photons of high-energy visible light or


Chap. 1, Chemistry, Green Chemistry, and Environmental Chemistry 
ultraviolet radiation, become energized (“excited”), and undergo reactions that lead to a
variety of products, such as photochemical smog. In addition to reactions that occur in the
gas phase, many important atmospheric chemical phenomena take place on the surfaces
of very small solid particles suspended in the atmosphere and in droplets of liquid in the
atmosphere. Although no significant atmospheric chemical reactions are mediated by
organisms in the atmosphere, microorganisms play a strong role in determining species
that get into the atmosphere. As examples, bacteria growing in the absence of oxygen,
such as in cows’ stomachs and under water in rice paddies, are the single greatest source
of hydrocarbon in the atmosphere because of the large amounts of methane that they

emit. The greatest source of organic sulfur compounds in the atmosphere consists of
microorganisms in the oceans that emit dimethyl sulfide. Atmospheric chemistry is
addressed specifically in Chapter 8, “Air and the Atmosphere.”
Chemical processes that occur in the geosphere involving minerals and their
interactions with water, air, and living organisms are addressed by the topic of
geochemistry. A special branch of geochemistry, soil chemistry, deals with the chemical
and biochemical processes that occur in soil. Aspects of geochemistry and soil chemistry
are covered in Chapter 10 of this book, “The Geosphere, Soil, and Food Production: The
Second Green Revolution in Agriculture.”
Environmental biochemistry addresses biologically mediated processes that occur
in the environment. Such processes include, as examples, the biodegradation of organic
waste materials in soil or water and processes within biogeochemical cycles, such as
denitrification, which returns chemically bound nitrogen to the atmosphere as nitrogen
gas. The basics of biochemistry are presented in Chapter 5, “The Wonderful World of
Carbon: Organic Chemistry and Biochemicals,” and in Chapter 9, “The Biosphere:
How the Revolution in Biology Relates to Green Chemistry.” Chapter 12, “Feedstocks:
Maximum Utilization of Renewable and Biological Materials,” discusses how chemical
processes carried out by organisms can produce material feedstocks needed for the
practice of green chemistry. The toxic effects of chemicals are of utmost concern to
chemists and the public. Chapter 13, “Terrorism, Toxicity, and Vulnerability: Chemistry
in Defense of Human Welfare,” deals with aspects of these toxic effects and discusses
toxicological chemistry.
Although there is not a formally recognized area of chemistry known as “anthrospheric
chemistry,” most of chemical science and engineering developed to date deals with
chemistry carried out in the anthrosphere. Included is industrial chemistry, which is
very closely tied to the practice of green chemistry. A good way to view “anthrospheric
chemistry” from a green chemistry perspective is within the context of industrial
ecology. Industrial ecology considers industrial systems in a manner analogous to natural
ecosystems. In a system of industrial ecology, various manufacturing and processing
operations carry out “industrial metabolism” on materials. A successful industrial

ecosystem is well balanced and diverse, with various enterprises that generate products
for each other and use each other’s products and potential wastes. A well-functioning
industrial ecosystem recycles materials to the maximum extent possible and produces
little — ideally no — wastes. Therefore, a good industrial ecosystem is a green chemical
system.


 Green Chemistry, 2nd ed

1.4. ENVIRONMENTAL POLLUTION
Environmental chemistry has developed in response to problems and concerns
regarding environmental pollution. Although awareness of chemical pollution had
increased significantly in the two decades following World War II, the modern
environmental movement dates from the 1962 publication of Rachel Carson’s classic
book Silent Spring. The main theme of this book was the concentration of DDT and
other mostly pesticidal chemicals through the food chain, which caused birds at the end
of the chain to produce eggs with soft shells that failed to produce viable baby birds. The
implication was that substances harming bird populations might harm humans as well.
Around the time of the publication of Silent Spring another tragedy caused great
concern regarding the potential effects of chemicals. This was the occurrence of
approximately 10,000 births of children with badly deformed or missing limbs as a result
of their mothers having taken the pharmaceutical thalidomide to alleviate the effects of
morning sickness at an early stage of pregnancy.
The 1960s were a decade of high concern and significant legislative action in the
environmental arena aimed particularly at the control of water and air pollutants. By
around 1970, it had become evident that the improper disposal of chemicals to the
geosphere was also a matter of significant concern. Although many incidents of such
disposal were revealed, the one that really brought the problem into sharp focus was
the Love Canal site in Niagara Falls, New York. This waste dump was constructed in an
old abandoned canal in which large quantities of approximately 80 waste chemicals had

been placed for about two decades starting in the 1930s. It had been sealed with a clay
cap and given to the city. A school had been built on the site and housing constructed
around it. By 1971 it became obvious that the discarded chemicals were leaking through
the cap. This problem led eventually to the expenditure of many millions of dollars to
remediate the site and to buy out and relocate approximately one thousand households.
More than any other single incident the Love Canal problem was responsible for the
passage of legislation in the U.S., including Superfund, to clean up hazardous waste sites
and to prevent their production in the future.
By about 1970 it was generally recognized that air, water, and land pollution was
reaching intolerable levels. As a result, various countries passed and implemented laws
designed to reduce pollutants and to clean up waste chemical sites at a cost that has
easily exceeded one trillion dollars globally. In many respects, this investment has been
strikingly successful. Streams that had deteriorated to little more than stinking waste
drainage ditches (the Cuyahoga River in Cleveland, Ohio, once caught on fire from
petroleum waste floating on its surface) have been restored to a healthy and productive
condition. Despite a much increased population, the air quality in smog-prone Southern
California has improved markedly. A number of dangerous waste disposal sites have been
cleaned up. Human exposure to toxic substances in the workplace, in the environment,
and in consumer products has been greatly reduced. The measures taken and regulations
put in place have prevented devastating environmental problems from occurring.


Chap. 1, Chemistry, Green Chemistry, and Environmental Chemistry 
Initially, serious efforts to control pollution were based on a command and control
approach, which specifies maximum concentration guideline levels of substances that can
be allowed in the atmosphere or water and places limits on the amounts or concentrations
of pollutants that can be discharged in waste streams. Command and control efforts to
diminish pollution have resulted in implementation of various technologies to remove
or neutralize pollutants in potential waste streams and stack gases. These are so-called
end-of-pipe measures. As a result, numerous techniques, such as chemical precipitation

of water pollutants, neutralization of acidic pollutants, stack gas scrubbing, and waste
immobilization have been developed and refined to deal with pollutants after they are
produced.
Release of chemicals to the environment is now tracked in the U.S. through the Toxics
Release Inventory TRI, under requirements of the Emergency Planning and Community
Right to Know Act, which requires that information be provided regarding the release
of more than 300 chemicals. The release of approximately one billion kilograms of
these chemicals is reported in the U.S. each year. Not surprisingly, the chemical industry
produces the most such substances, followed by primary metals and paper manufacture.
Significant amounts are emitted from transportation equipment, plastics, and fabricated
metals, with smaller quantities from a variety of other enterprises. Although the quantities
of chemicals released are high, they are decreasing, and the publicity resulting from the
required publication of these releases has been a major factor in decreasing the amounts
of chemicals released.
Although much maligned, various pollution control measures implemented in
response to command and control regulation have reduced wastes and improved
environmental quality. Regulation-based pollution control has clearly been a success
and well worth the expense and effort. However, it is much better to prevent the
production of pollutants rather than having to deal with them after they are made. This
was recognized in United States with the passage of the 1990 Pollution Prevention Act.
This act explicitly states that, wherever possible, wastes are not to be generated and their
quantities are to be minimized. The means for accomplishing this objective can range
from very simple measures, such as careful inventory control and reduction of solvent
losses due to evaporation, to much more sophisticated and drastic approaches, such as
complete redesign of manufacturing processes with waste minimization as a top priority.
The means for preventing pollution are best implemented through the practice of green
chemistry, which is discussed in detail in the following section.
1.5. WHAT IS GREEN CHEMISTRY?
The limitations of a command and control system for environmental protection have
become more obvious even as the system has become more successful. In industrialized

societies with good, well-enforced regulations, most of the easy and inexpensive measures
that can be taken to reduce environmental pollution and exposure to harmful chemicals
have been implemented. Therefore, small increases in environmental protection now
require relatively large investments in money and effort. Is there a better way? There is,
indeed. The better way is through the practice of green chemistry.